Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material



of the original.

Patented Jan. 9, 1951 POLY-ACETOACETYL DERIVATIVES OF POLYAMINES AS AZO COMPONENTS IN DIAZOTYPE PHOTOPRINTING MATE- RIAL William H. von Glahn, Londonville, and Lester N. Stanley, Delmar, N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.

9 Claims.

This invention relates to a diazotype process and more particular y to the use of certa-n azo components in the light-sensitive layer of a diazotype reproduction medium or in a developing solution for the exposed diazotype image.

In the reproduction of mechanical drawings, printed material, pictures or other orig nals to be copied, it is of particular advantage in many cases to make first an intermediate print or transition print on a transparent diazotype copying material by exposing the transparent sensit zed diazotype material to actinic ravs such as ultraviolet light by either the printing through or reflex process and then deve oping the diazotype material. The development of such diazotype prints may be carried out by any of the developing methods known to the art for develop-- ment of exposed diazotype materials. Thus, Where a two-component system is empoyed containing the azo component in the light-sensitive layer with the diazo compound, development is effected by passing the exposed diazotype through ammonia vapors, and Where a one-component system is employed which contains the diazo compound as the only dye component in the lieht-senstive layer, the image is developed by treating the exposed diazotype with an alkaline solution containing the azo component by a dipping or fog spraying method. The ima e thus produced on the transparent intermediate or transition diazotype print can be used for reproduction of further dazotype prints of hi h'contrast. If desired. they can also be used for the reproduction of the image on any suitable photoprinting material such as silver halide photographic paper and Van Dyke prints and blueprints.

This method ofproducing transition diazotype prints is particularly useful when it is desired to make a number of reproductions from a frail or valuable original which would be adversely afiected if not destroyed in the repeated exposures necessary to make the desired number of copies. It is essential in the so-oalled reflex process where the diazotype copy material is superimposed on the opaque original to be coped and.

the light for exposure of the diazotype material passes through it and is reflected by the surface The efficiency of the process involving the production of a transition or intermediate print depends upon the opac ty of the azo dye image produced upon such intermediate or transition print to ultraviolet light and upon the transparency of the background to such light. It depends also upon the visual density of Application October 18, 1946, Serial No. 704,302

the image produced on the intermediate or transition print s nce images of poor visual density such as light yellows on a white or transparent. background, though they may have the desired degree of opacity to ultraviolet light nevertheless have the disadvantage of rendering difficultthe detection of flaws in the intermediate image. With such prints, it is necessary to make a contrast printof good visual density from the intermediate before such flaws can be detected thereby introducing an additional and unnecessary step.

Prints of a deep color having good visual density can be obtained from diazotypes using azo components common to the art for the production of ord nary diazotypes such as phloroe lucin,v 2.3-dihydroxynaphthalene and B-naphthol-3,6. disulfonio acid. However, despite the goods visual density of-the color reproducing the image, its actinic opacity or photographic density is not sufiicient to reproduce the image sat sfactorily, in subsequent copies. The azo dye component used for the production of transition print images must be suchas to roduce upon coup ing with the diazo compound employed a color which Will sufficiently absorb the-ultraviolet light incident upon t during exposure to prevent lightdecomposition of the diazo compound in the areas Colors of good visual density do not necessarily have this property. It is well known for instance that blues such as are produced from azo components like ph orogl'ucin are very poor in their ultraviolet absorption character stics.

Azo components such as resorcinol have heretofore been employed in the production of d azotype prints in order to obtain color images having the necessary li ht absorption characteristics for transition printing. Resorcinol will reproduce the image on the transition print in a sepia or orange-brown color which has good opacity to ultraviolet light and has sufilcient depth of color or visual density to assure detection of printing flaws and the like in the developed intermediate print. Other azo components have been sug e ted which will produce mages of good opacity or covering power when used in combination with poly hydroxy azo com onents such as phloroglucinol and resorcinol. These azo components are acetoacetyl derivatives of monoamines and are disclosed in Patent #1,989,065.

However, although these acetoacetvl derivatives of mono-amines may produce satisfactory results as shaders for other colors which may lack the necessary covering power, particularly in copying half tones or too light lines, they do not produce satisfactory images when used as self colors, that is, when the acetoacetyl derivatives of monoamines such as the cyclohexyl acetoacetic acid amide and the like disclosed in Patent #l,989,065 are used as the only azo components for the development of a diazotype print, the image produced does not have a satisfactory shade or tone value.

It has now been found that the polyacetoacetyl derivatives of aliphatic. aromatic or heterocyclic polyamines are especially effective as azo components or diazotype reproductions. This class of azo components can be used satisfactorily either alone in the production of self shades or in combination with other azo components for shading purposes. In either case the resulting images have excellent opacity characteristics. The opacity to ultraviolet light and covering power of the self shades markedly surpass those properties of colors produced from the monoacetoacetyl derivatives and when used for shading purposes in combination with such azo com onents as phloroglucinol, 2.3-dihydroxv naphthalene or 2.3- dihydroxy naphthalene sulfonic acid, excellent neutral blacks having good opacity to ultraviolet light are obtained. In general these polvacetoacetyl derivatives are prepared from the corresponding polyamine by reaction with acetoacetic esters or with diketines. The acetoacetic ester or diketene condenses with the amino groups of the poly amine thus forming amide linkages. The amine may be any aliphatic, aromatic or heterocyclic polvamine wherein the al phatic chain or aromatic or heterocyclic nuclei may be substituted by any of the usual substituents such as alkyl, halogen, alkoxy, carboxy, sulfo, hydroxy or other groups which do not discolor the paper or impair the solubility characteristics of the azo component. (For example, nitro groups discolor the paper.) This class of azo components may be represented by the following general formula: R(COCH2COCH3) 11, wherein R is an aliphatic aromatic or heterocyclic polyamino radical and n is a whole number greater than one and each acetoacetyl group is attached to an amino nitrogen atom of R. Examples of polyacetoacetyl derivatives of this class are:

1. N-(B-acetoacetaminoethyl) -acetoacetamide CHE-NBC (311200 CH:

CHr-NHC O CHzC OCH:

I 2. N-(B-acetoacetaminopropyl)-acetoacetamide 3. N,N' (acetoacetylimino diethylene) diacetoacetamide CHzCHr-NHCO CHzCOCHa N-CO CHzC 0 CH3 CHiCHr-NHOOCHrCO CH3 4. 2,4-diacetoacetamino-benzene sulfonic acid S'OSH NH0 0 CHaO O CH:

NHCOOHzCOCH'a 5. 2,4-diacetoacetamino-toluene NHCOCHnO OCH:

NHCO CHZC 0 CHi 6. Bis-acetoacet-oor m-dianisidide CHaCOCHzCONH- NHCOCHzCOCHs 7. Diacetoacetyl-piperazine 9. 'I'riacetoacetyl-melamine CHaC 0 cine GEN-{'1 l IHCOCHzCO CH:

10. Diacetoacetyl-benzidine CH3C o omc OHN-OONHC come 00m 11. 1,4-diacetoacetamino-naphthalene (ll-NEG O CHzCO CH3 CHaCOOHzCOHN NHCOCHECOCHS In the preparation oi di'azotype materials intended for use as intermediate or transition print media in accordance with this invention, a suiitable transparent base such as transparentized paper, cellulose acetate film or other transparent material is coated by means known to the art with a light-sensitive composition containing suitable diazo compounds. Where it is desired to make a two-component diazotype layer on the support or base material for development by the dry developing method, the azo component is also incorporated into the coating composition. Where one-component diazotype layers are desired, the azo component is added to an alkaline developing solution and after exposure of the diazotype the exposed image is developed by contacting with the alkaline developing solution by means known to the art. In the preparation of coating compositions for two-component diazotype layers, the coating solution may also contain such other materials as are ordinarily used in the preparation of diazotype two-component light-sensitive coating compositions. These include stabilizing materials such as citric acid, phosphoric acid and thiourea; swelling agents for cellulose acetate and other cellulosic ester bases such as isopro- 'panol, and shade intensifying agents, such as nickel sulfate. In the preparation of light-sensitive layers on paper for the production of neutral black images or dark tone images which may or may not be intended for reproduction of further copies, it is preferable to employ a two-component coatin composition which will contain amine;

one or moredark tone producing azo components, preferably such as will produce blue shades with the diazo compounds employed in combination with the polyacetoacetyl amino azo components of this invention. The diazo compound or compounds and other adjuvants are added to the coating composition and the paper used as a carrier for the light-sensitive layer is coated in the same manner as the. transparentized paper or cellulosic film base material in the case of the transition print media. As diazo compounds any suitable light-sensitive diazo compound which will couple with the azo components to reproduce a colored image may be employed. We prefer, however, to use diazo compounds derived from p-diamines of the benzene series, particularly when two-component coating compositions are employed. As is well known in the art, this class of diazo compounds is especially suitable for the production of two-component diazotype photo-sensitized papers. Other diazo compounds have been found suitable for use such as diazo anhydrides of aminohydroxynaphthalene compounds but are less extensively employed. The

p-diamines most generally used for production of the diazo compounds are those wherein one'of the amino groups is unsubstituted for diazotization and the other is substituted by such groups as alkyl, alkoxy-alkyl, aryl, aralkyl, alkylol, cycloaliphatic and heterocyclic groups. Examples of these amines from which the diazo compounds are derived include N-hydroxyethyl-N-methylamino-p aminobenzene; p amino diphenyll-mono-methylamino-2 (or 3) -methyl-4- aminobenzene; 1-N-hydroxyethyl-N-ethylamino- 3-methyl-4-aminobenzene; 1-diethylamino-3-ethoxy--aminobenzene; 4-amino-1-benzoylamino- 2,5-diethoxybenzene; p-amino -N-diethylaniline; 1-N,N-dihydroxyethylamino 3 chloro-4-aminobenzene; p-arnino-N-ethyl-N-benzylaniline; lethyl-4-aminobenzene; 1-N-hydroxyethyl-Nethylamino-4-aminobenzene; p-phenylene diamine; 4-amino-N,N-dihydroxyethylaniline; p- (4- ethoxy phenyl) amino-2,5-diethoxyaniline; l-N-ethylamino-2-methyl-4-aminobenzene; l-dimethylamino-3-methoxy-4-aminobenzene; N,N-dimethylamino p aminobenzene; l-dimethylamino-3- methyll-aminobenzene; p-aminophenyl morpholine and 2amino-1-naphthol-5-sulfonic acid. The diazo derivatives of these amines are used in the form of their stabilized salts, such as the Z11C12, CdClz or SnClz double salts, fiuoro borates, aryl or alkyl sulfonates, and acid sulfates of the diazonium chloride.

The following specific examples will serve to illustrate further the invention, it being understood, however, that they are not intended to limit its scope. Unless otherwise stated, the parts are by weight.

Example I Transparentized paper is coated with a coating solution containing the following materials per 100 cc. of a 5% aqueous solution of alcohol:

3.5 g. N-(fi-acetoacetaminoethyl) -acetoacetamide 3.8 g. N -methyl, N-hydroxyethylamino-p benzene diazonium chlolide-ZnCh double salt 40 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride 1 The coated transparency is first dried in the usual manner. It is then exposed to actinic light 1 under a pattern and developed by contacting with ammonia fumes. The image of the pattern is de- This print has excellent qualities of opacity to ultraviolet light in the dye areas and is, there- .fore, eminently suited to further reproduction work. The dye image of this transparency is also .highly resistant to fading so that a large number of reproduction can be made from it and it has good wash-fastness properties.

Example II Transparentized paper is coated with a coating solution containing the following ingredients per cc. of a 5% aqueous solution of alcohol:

3.5 g. N- (p-acetoacetaminoethyl) -acetoacetamide 13.5 g. N,Ndiethylamino-p-benzene diazonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride The coated transparency is first dried in the usual manner and is then exposed to light under a pattern and developed by contacting with ammonia fumes. The image of the pattern is developed in a deep orange sepia shade which possesses excellent opacity to ultraviolet light. It is there fore Well suited for further reproduction work as a transition print. Its light-fastness and washfastness properties are similar to the prints obtained in accordance with Example I.

Example III Transparentized paper is coated With a coating solution containing the following ingredients per 100 cc. of a- 5% aqueous solution of alcohol:

' 3.5 g. N- (fl-acetoacetaminoethyl) -acetoacetamide 3.6 g. 1-N-ethylamino, 2-methyl-4-benzene diaZonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid .2.0 g. phosphoric acid 5.0 g. zinc chloride are also good and it i particularly suited for use as a transition print in the reproduction of further copies.

Example IV Transparentized paper is coated with a coating solution containing the following ingredients per *100 cc. of a 5% aqueous solution of alcohol:

: 5.8 g. N- (B-acetoacetaminopropyl) -acetoacetamide 3.8 g. N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride-ZnCl; double salt.

4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride The coated transparency is first dried in the usual manner and is then exposed under a pattern and developed by contacting with ammonia fumes. The image of the pattern is reproduced I -in an orange-yellow print. This transition print possesses excellent opacity to ultraviolet light in the dye areas and is therefore particularly suited for further reproduction work. Its light-fastness and wash-fastness properties are also good.

Upon substituting 4.0 g. 1-(n-ethylamino)-2- methyl-4-benzene diazonium chloride-ZnClz double salt or 4.5 g. N-ethyl, N-hydroxyethylaminop-benzene diazonium chloride-ZnClz double salt for the 3.8 g. N-methyl, N-hydroxyethylamino-pbenzene diazonium chloride-ZnClz double salt of this example, orange-yellow prints of outstanding opacity characteristics having the same light- -fastness and Wash-fastness properties as the prints of this example, may be obtained.

Example V Transparentized paper is coated with a coating solution containing the following ingredients per 100 cc. of a 5% aqueous solution of alcohol:

2.3 g. N,N- (acetoacetyliminodiethylene) -diacetacetamide 3.8 g. N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride-ZnCh double salt 4.0 g. thiourea -8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride opacity to ultraviolet light.

Upon substituting 3.5 g. N-phenylamino-pbenzene diazonium acid sulfate for the 3.8 g. N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride-ZnClz double salt of this example, brown prints having excellent opacity characteristics are obtained.

Example VI Transparentized paper is coated with a coating solution containing the following ingredients per 100 cc. in a aqueous solution of alcohol:

7.0 g. 2,4-diacetoacetamino-benzene sulfonic acid 3.8 g. N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride tained.

Example VII Transparentized paper is coated with a 5% solution of 1-benzoy1amino-2,5-diethoxy-4-benzene diazonium chloride-ZnClZ double salt in cc. of water containing 5% alcohol, 4% thiourea and 0.5% saponin.

The coated transparency is first dried in the usual manner and then exposed to light under a pattern. The print is developed moist by applying a 5% solution of (N-(fl-acetoacetaminoethyD-acetoacetamide containing 5 g. of NazCOa per 100 cc. of solution.

The sepia print of the pattern thus obtained has outstanding opacity characteristics. It also has good light-fastness and wash-fastness properties.

Example VIII Ordinary paper stock for diazotypes is coated with a coating solution containing the following .ingredients per 100 cc. of a 3% aqueous solution of isopropanol:

1.4 g. N (B acetoacetaminoethyl) acetoacetamide 3.0 g. 2,3-dihydroxynaphthalene-6-sulfonic acid 0.15 g. 2,3-dihydroxynaphthalene 3.0 g. N,N-diethylarnino-p-benzene diazonium chloride-ZnClz double salt 5.0 g. ZnClz 10.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. thiourea The coated paper is first dried in the usual manner and is then exposed under a pattern and developed by contacting with ammonia fumes. The prints thus developed are a neutral black shade having good gradation and showing little tendency for color shift upon standing. These prints also have good opacity to ultraviolet light and good light-fastness and wash-fastness properties.

Upon substituting the following mixtures of azo components for the three azo components in the formula. of this example, diazotype prints having similar characteristics and properties are obtained:

(1) 1.0 g. 2,4-diacetoacetamino-toluene 3.0 g. 2,3 dihydroxynaphthalene-6-sulfonic acid 0.12 g. 2,3-dihydroxynaphthalene (2) 1.0 g. bis-acetoacet-o-dianisidide 2.8 g. 2,3 dihydroxynaphthalene-fi-sulfonic acid 0.1 g, 2,3-dihydroxynaphthalene The coating, formula and procedure are otherwise the same as in this example. The compositions of this example illustrate the utility of the polyacetoacetyl polyamines of this invention for shading to neutral blacks when they are used in mixture with azo components which normally developto a blue shade. Other azo components which will develop blue shades, such as phloroglucinol, may be substituted for or combined with the 2,3-dihydroxynaphthalene couplers of this example with similar results and azo components which will produce tones other than blue may also be used in combination with the polyacetoacetyl polyamines to produce modified tones which will have good covering power and opacity to ultraviolet light.

We claim:

1. A diazotype photoprinting material comprising a light-sensitive diazo compound and an azo component selected from the class consisting CH2NHC O CHzC CH3 H2NHOO CHzC OCHs 4. A diazotype photoprinting material comprising a light-sensitive diazo derivative of a pdiamine of the benzene series and as azo component the compound N-(fl-acetoacetaminoethyD-acetoacetamide having the structural formula:

OH2-NHO O 0112C 0 CH3 CHz-NHC O OHzG 0 CH1 5. A diazotype photoprinting material comprising a salt of N-diethylamino-p-benzene diazonium chloride and N-(B-acetoacetaminoethyl) -acetoacetamide having the structural formula:

CHz-NHO 0 01120 0 CH3 Hz-NHC O OHzO 0 CH3 6. A diazotype photoprinting material comprising a salt of N,N-diethylamio-p-benzene diazonium chloride, N- (fl-acetoacetaminoethyl) acetoacetamide, 2,3-dihydroxynaphthalene and 2,3-dihydroxynaphthalene-6-sulfonic acid.

7. A diazotype photoprinting material comprising a light-sensitive diazo compound and as azo component the compound N,N-(acetoacetylimino diethylene) diacetoacetamide, having the structural formula:

8. A diazotype photoprinting material com prising a light-sensitive diazo derivative of a pdiame of the benzene series and as azo component the compound N,l l (acetoacetyliminodiethylene) -diacetoacetamide, having the structural formula:

CHzCHzNHCOOH2COCHa NCOOHzCOCHs fizCHz-NHOOGEzCOOHa 9. A diazotype phctoprinting material comprising a salt of N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride and N,N- (acetoacetylimino-diethylene) -diacetoacetamide, having the structural formula:

CHZOHPNHC o QHZC 0 CH3 NCOCH2COOH3 HzCH2NHC o CHzC 0 CH3 WILLIAM H. VON GLAHN. LESTER. N. STANLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,822,065 Sprongerts Sept. 8, 1931 1,972,323 Shiraeif A Sept. 4, 1934 1,989,065 Schmidt Jan. 22, 1935 2,010,884 Olpin Aug. 13, 1935 2,027,229 Hinman Jan. 7, 1936 2,250,129 Kopp et a1 July 22, 1941 2,299,641 Middleton Oct. 20, 1942 2,312,040 Kendall Feb. 23, 1943 2,331,812 Steiger Oct. 12, 1943 2,395,776 Bavley Feb. 26, 1946 OTHER REFERENCES Spencer: Photographic Applications of Diazo Compounds, The Photographic Journal (London), December 1928, pages 490 to 496, page 494 cited (copy in S. L.). 

1. A DIAZOTYPE PHOTOPRINTING MATERIAL COMPRISING A LIGHT-SENSITIVE DIAZO COMPOUND AND AN AZO COMPONENT SELECTED FROM THE CLASS CONSISTING OF POLYACETOACETYL DERIVATIVES OF ALIPHATIC POLYAMINES WHEREIN THE ACETOACETYL GROUPS ARE ATTACHED TO AMINO NITROGEN ATOMS OF THE POLYAMINES. 